CN1529385A - Chargeable lithium ion cell polymer electrolyte and preparing method thereof - Google Patents
Chargeable lithium ion cell polymer electrolyte and preparing method thereof Download PDFInfo
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- CN1529385A CN1529385A CNA2003101078490A CN200310107849A CN1529385A CN 1529385 A CN1529385 A CN 1529385A CN A2003101078490 A CNA2003101078490 A CN A2003101078490A CN 200310107849 A CN200310107849 A CN 200310107849A CN 1529385 A CN1529385 A CN 1529385A
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Abstract
In the invention, polymer dielectric instead of liquid electrolyte is applied to lithium cell to produce cell in different shapes with performances of safety, lightweight and high energy density. In contrast, in prior art, there are disadvantages such as unstable liquid and bad mechanical properties in existed technique. Gel state inorganic-organic hybrid polymer dielectric is prepared through ultraviolet light radiation to trigger off polymerization. The polymer dielectric is amorphous in room temperature possessing features of high conductivity, stable thermal and mechanical properties. Advantages of ultraviolet light solidifying method are one-step molding, simple technique, high efficiency, no pollution. Performed polymer of inorganic-organic hybrid polymer is prepared by reconstructing end group after sol-gel reaction of alkoxyl silicon compound. In room temperature, ionic conductivity is reached to 8.4x10 to the power -3 Scm being close to conductivity of liquid electrolyte.
Description
Technical field
The present invention is a kind of chargeable lithium ion battery polymer dielectric and preparation method thereof.
Background technology
Lithium ion battery because of it has the specific power height, energy density is big, operating voltage is high, in light weight, volume is little, advantage such as nontoxic, pollution-free, on portable electric appts such as notebook computer, mobile phone, obtained using widely.The employed electrolyte of lithium ion battery is the nonaqueous electrolytic solution that contains lithium salts basically at present, has existed shortcomings such as the phenomenon of leakage, fail safe is not good enough.(solid polymer electrolytes SPEs) replaces the research work of liquid electrolyte with copolymer solid electrolyte so people just are being devoted to.Polymer dielectric is electrolyte in battery, has played barrier film simultaneously again.Polymer dielectric is applied to lithium ion battery and helps preparing safety, light weight, high-energy-density and different battery.
The polymer dielectric of research is broadly divided into three classes at present: full solid state polymer electrolyte (dry SPEs), gel polymer electrolyte (gelled SPEs), porous type polymer dielectric (porous SPEs).Full solid state polymer electrolyte mainly is made up of polymer, lithium salts and a small amount of additive, owing to there is not the existence of liquid electrolyte, the fail safe of lithium battery improves greatly.But the full solid state polymer electrolyte room-temperature conductivity is too low, is generally 10
-7-10
-4Scm
-1, limited its commercial application.The porous type polymer dielectric is representative (U.S.patent 5,540,741) with the invention of U.S. Bellcore company, has tentatively realized commercialization, and the preparation method is complicated.Gel polymer electrolyte is to be wrapped in the polymer with the lithium salts electrolyte by liquid lithium ionic cell to form, its conductivity at room temperature height, preparation is simple, be research at present extensively and be hopeful at once can a commercial base polymer electrolyte.Gel state and porous type polymer dielectric contain a large amount of liquid plasticizers, though conductivity is higher, also have shortcomings such as bag liquid instability, bad mechanical property.
Summary of the invention
The objective of the invention is chargeable lithium ion battery polymer dielectric that makes conductivity height, stable performance and preparation method thereof.
Chargeable lithium ion battery polymer dielectric of the present invention is composed as follows:
The polymer that polyacrylate based oxyalkylsiloxane (PAAOS) forms: 5-90wt.%
Chargeable lithium ion battery liquid electrolyte: 10-95wt.%
The structure of PAAOS formula [SiO
d(OH)
e(OR
2)
f(O (CH
2CH
2O) nCOCR
1=CH
2)
g]
kExpression, R
1=H or CH
3, n=1～7, R
2=CH
3, CH
2CH
3
Add an amount of polyethyleneglycol diacrylate (PEGDA) in the electrolyte formula of the present invention, the polymer of formation can improve the fragility of polymer dielectric, and the content of each component is as follows:
The polymer that PAAOS and polyethyleneglycol diacrylate (PEGDA) form: 8-90wt.%;
PEGDA accounts in the polymer that forms: 17-67wt.%;
Chargeable lithium ion battery liquid electrolyte: 10-92wt.%;
The molecular formula of PEGDA: CH
2=CR
1COO (CH
2CH
2O)
nCOCR
1=CH
2, R wherein
1=H or CH
3, n=3～16.
What the present invention prepared is a kind of gel state inorganic-organic hybridization polymer dielectric.The performed polymer of inorganic-organic hybridization polymer mixes after the ultraviolet radiation polymerization prepares gel polymer electrolyte with lithium ion battery liquid electrolyte, light trigger.(poly (ethylene glycol) diacrylates PEGDA) can improve the fragility of polymer dielectric to add an amount of polyethyleneglycol diacrylate in prescription.In the inorganic-organic hybridization polymer, inorganic part is to link to each other with chemical bond with organic moiety, has Stability Analysis of Structures, hot property and stable mechanical performance, shrinkage is little before and after the polymerization, dimensionally stable, bag liquid ability reaches the conductivity advantages of higher by force, so the inorganic-organic hybridization polymer is a kind of material of desirable preparation polymer dielectric.
Polymer dielectric of the present invention prepares by UV-curing technology, one step processing, and technology is simple, efficient is high, pollution-free.
The performed polymer of the inorganic-organic hybridization polymer that the present invention is used prepares by two-step method, the first step is gathered oxyalkylsiloxane (polyalkoxysiloxane with alkoxy-silicon compound by the sol gel reaction preparation, PAOS), second step was converted to acrylate-based with the alkoxyl end group that the acrylate compounds of hydroxyl will gather oxyalkylsiloxane, thereby obtain ultraviolet curing prepolymer polyacrylate based oxyalkylsiloxane (polyacrylalkoxysiloxane, PAAOS).
1. the preparation of gel state inorganic-organic hybridization polymer dielectric
The performed polymer PAAOS and the light trigger of uV curable are mixed, mix with the lithium ion battery liquid electrolyte of different amounts again, be coated onto on the sheet glass or directly be added drop-wise in the stainless steel button battery, through ultraviolet lighting 0.5-5 minute, make gel state inorganic-organic polymer electrolyte.
The lithium ion battery liquid electrolyte is: 1M LiPF
6, EC: DEC: DMC=1: 1: 1w/w; 1M LiPF
6, EC: DEC=1: 1w/w; 1M LiPF
6, EC: PC=1: 1w/w; 1M LiPF
6, EC: DEC: PC=1: 1: 1w/w; 1M LiPF
6, EC: DEC: DMC: VC=32: 32: 32: 4w/w, its consumption accounts for the 6wt.%-95wt.% of gel polymer electrolyte gross weight.
The polymer that PAAOS forms accounts for the 5wt.%-90wt.% of gel polymer electrolyte gross weight.Polymer can form gel state when content is 5wt.% in gel polymer electrolyte, and room-temperature conductivity is near the conductivity of used liquid electrolyte.PAAOS can form the three-dimensional network polymer through ultraviolet light irradiation, and its bag liquid ability is far longer than the polymer (content of polyethyleneglycol diacrylate is greater than 10wt.% just can form stabilizing gel with liquid electrolyte) that is formed by polyethyleneglycol diacrylate.And along with the increasing of performed polymer acrylate end groups, rate of polymerization increases, and bag liquid ability increases, but the fragility of polymer dielectric also increases thereupon.
Add an amount of polyethyleneglycol diacrylate (PEGDA) and can improve electrolytical fragility.The addition of PEGDA accounts for the 17-67wt% of polymerisable monomer weight.The molecular formula of PEGDA: CH
2=CR
1COO (CH
2CH
2O)
nCOCR
1=CH
2, R wherein
1=H or CH
3, n=3～16.The PEGDA consumption is understood the bag liquid ability and the electrolytical dimensional stability of impact polymer too much.(methoxy poly (ethylene glycol) is acrylate (meth), MPEGA) because curing rate is slower, should not add for polyethylene glycol (methyl) acrylate ether.PEGDA bag liquid ability is less than PAAOS, so the polymer of PAAOS and PEGDA formation accounts for the 8wt.%-90wt.% of gel polymer electrolyte gross weight.
Used light trigger is: 1-hydroxy-cyclohexyl acetophenone (trade name: Iragacure 184) or α, and alpha-alpha-dimethyl-Alpha-hydroxy acetophenone (trade name: Darocure 1173), the consumption of light trigger is generally the 4-8wt.% of polymerizable compound weight.The all available art methods of above-mentioned PAAOS, PEGDA obtains, and PEGDA has the commercial goods, and the also available following method of PAAOS obtains.
2. the preparation of ultraviolet curing prepolymer polyacrylate based oxyalkylsiloxane (PAAOS)
The preparation of performed polymer PAAOS was divided into for two steps, the first step is gathered oxyalkylsiloxane (polyalkoxysiloxane with alkoxy-silicon compound by the sol gel reaction preparation, PAOS), second step was converted to the alkoxyl end group of PAOS with the acrylate compounds of hydroxyl acrylate-based, obtained PAAOS.
2.1 the preparation of PAOS
Poly-oxyalkylsiloxane is that alkoxy-silicon compound is in the presence of solvent, catalyst, by sol gel reaction preparation.Product gathers the structure of oxyalkylsiloxane (PAOS) can use formula [SiO
a(OH)
b(OR)
c]
nExpression, R=CH
3, CH
2CH
3Carry out molecular weight, dioxide-containing silica, hydroxy radical content mensuration, can calculate a in the formula, b, c, the n value, thus the structure of determining the product molecule is formed.Structural representation as shown in Figure 1.
The most frequently used alkoxy-silicon compound has two kinds: methyl silicate (tetramethoxysilane, TMOS) and tetraethoxysilane (tetraethoxysilane, TEOS), molecular formula is respectively Si (OCH
3)
4, Si (OCH
2CH
3)
4The TEOS reactivity is less, and reaction speed is slower, is easy to control, good reproducibility, and the dioxide-containing silica of product is lower.The difficult control of TMOS reactivity height, reaction, reaction repeatability is relatively poor, gelation easily takes place, molecular weight of product wider distribution, but product dioxide-containing silica height.
The degree of hydrolysis of alkoxy-silicon compound is controlled by the addition of water.Degree of hydrolysis is meant that the methoxy radix of hydrolytic condensation accounts for the ratio of methoxyl group sum before the reaction, and during the whole hydrolytic condensation of alkoxyl, degree of hydrolysis is 100%.General selection degree of hydrolysis is 20～80%, and optimum value is 40～60%.Be lower than 20%, then level of residual monomers is many, and productive rate is low, is higher than 80%, and gel easily takes place.So the consumption of water generally is 0.4-1.6 times of the alkoxy-silicon compound molal quantity, preferably 0.8-1.2 doubly.
The hydrolysis-condensation reaction of alkoxy-silicon compound both can also can be used base catalysis with acid catalysis.Acid-catalyzed hydrolysis is fast and condensation is slow, and base catalysis is then just in time opposite.The particle that base catalysis obtains is many at micron order, and the particle that acid catalysis obtains is then below 100nm, and acid catalysis helps the control of granular size.Acid catalyst can be inorganic acid example hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid etc., also can be organic acid, as formic acid, acetate, maleic acid, benzene sulfonic acid etc.Base catalyst can be NaOH, potassium hydroxide, calcium hydroxide, ammonia, or organic metal, metal oxide, organo-tin compound etc.Catalyst consumption generally is 1 * 10 of an alkoxy-silicon compound molal quantity
-5To 1 * 10
-3Doubly.
Reaction dissolvent generally is organic solvents such as alcohol, ether, ketone, considers easily the removing property and the easily recovery property of solvent, the general selection and the identical solvent of alkoxy-silicon compound hydrolytic condensation accessory substance.Preferably select methyl alcohol to make solvent as the reaction of methyl silicate, the reaction of tetraethoxysilane preferably selects ethanol to make solvent.The amount of solvent is generally 0.1 to 10 times of reactant weight, is preferably 0.5 to 1 times.
Reaction temperature is generally near the boiling point of solvent or the boiling point of accessory substance, and the reaction time was generally 0.1 to 10 hour, mostly at 1 to 5 hour.
Alkoxy-silicon compound is poisonous, and flash-point is low, and steam stimulates eyes, and its activity is bigger, if remnants are arranged, the storage stability of product is reduced, and influence the performance of material in curing formula.Generally require the residual monomer amount in the product had better not surpass 0.3wt% less than 1%.The method of removing residual monomer has: flash distillation, vacuum distillation or be blown into inert gas such as N
2, CO
2, Ar, He etc.
2.2 the preparation of PAAOS
Acrylate compounds with hydroxyl makes the part end group of PAOS become can react acrylate-based by ester exchange reaction, obtains photo curable product polyacrylate based oxyalkylsiloxane (PAAOS).Ester exchange reaction is simple to operate, need not solvent, and the ratio of acryloyl group is easy to control in the product end group, helps the control of crosslink density.
The structure of PAAOS can be used formula [SiO
d(OH)
e(OR
2)
f(O (CH
2CH
2O)
nCOCR
1=CH
2)
g]
kExpression, wherein R
1=H or CH
3, n=1～7, R
2=CH
3, CH
2CH
3Measure by carrying out molecular weight, dioxide-containing silica, hydroxy radical content, can calculate the value of d, e in the formula, f, g, k, thereby the structure of determining the product molecule is formed.Structural representation as shown in Figure 2.
The acrylate compounds molecular formula of hydroxyl is: HO (CH
2CH
2O)
nCOCR
1=CH
2, R wherein
1=H or CH
3, n=1～7.N hour, viscosity is less, reaction speed is fast, conversion ratio is higher, remaining reactant easily decompression is removed.Work as R
1=H is acrylic acid-2-hydroxyl ethyl ester (HEA) during n=1, is the more reactant of selecting for use.When n was big, the ethylene oxide segment was more, and resulting polymers fragility is less, but Residual reactants difficulty remove.
The consumption of the acrylate compounds of hydroxyl generally is 1-8 a times of PAOS molal quantity, and preferably 2-5 doubly.Consumption very little, then the functional group of the photopolymerization of product P AAOS is difficult to form three-dimensional net structure preferably very little, bag liquid ability drop; Consumption is too many, and conversion ratio descends, and the functional group of the photopolymerization of product P AAOS is too many, and the polymer of formation is too crisp.
Ester exchange reaction need not solvent, must add catalyst and polymerization inhibitor, reaction temperature 80-90 ℃.Catalyst generally is the organic tin compound, as dibutyl tin laurate, dibutyltin diacetate.Polymerization inhibitor can be selected hydroquinone monomethyl ether, quinhydrones, hydroquinones etc. for use.Reaction temperature 80-90 ℃, temperature is too high, and polymerization or gel may take place, and temperature is too low, and then reaction is too slow, and conversion ratio is low.
Electrolyte of the present invention is mainly used in the electrolyte and the material thereof that can fill lithium or lithium ion battery.
The present invention is by the gel state inorganic-organic hybridization polymer dielectric of UV-curing technology preparation, have hot property and stable mechanical performance, shrinkage is little before and after the polymerization, dimensionally stable, the bag liquid measure reaches the conductivity advantages of higher greatly, one step processing during preparation, technology is simple, efficient is high, pollution-free.
Description of drawings
Fig. 1 is poly-oxyalkylsiloxane (PAOS) structural representation.
Fig. 2 is polyacrylate based oxyalkylsiloxane (PAAOS) structural representation
Embodiment
Example 1: the preparation of polymethoxy siloxanes (PMOS)
In the four-hole reaction bulb of thermometer, mechanical agitation, return duct is housed, put into 152gTMOS (1mol) and 128g methyl alcohol, mix.With moisture 18g, HCl 2 * 10
-4The hydrochloric acid of mol is put into dropping funel.Under the vigorous stirring, the salt slow acid is splashed in the reaction bulb, need 1 hour approximately.After dropwising, be warming up to reflux temperature.After the back flow reaction 2 hours, steam methyl alcohol to 130 ℃.Temperature is risen to 150 ℃ then, feed dry nitrogen current, kept 3 hours.Cool to room temperature obtains the liquid product PMOS 104.0g of achromaticity and clarification, reaction yield 97.2%.Through characterizing the afterproduct molecular weight is 1027, and molecular structure can be expressed as [SiO
0.9769(OH)
0.0585(OCH
3)
1.991]
9.650
In the preparation of polymethoxy siloxanes, the amount difference of water, reaction yield and molecular weight of product are also different, as shown in table 1 with molecular formula.
The amount of table 1 reactants water, reaction yield and product P MOS molecular weight and molecular formula
PMOS H
2O/TMOS productive rate weight molecule formula
(molar (％) Mn
ratio)
S-1 0.8 81.5 746 [SiO
0.7750(OH)
0.1050(OCH
3)
2.345]
6.487
S-2 0.9 89.6 846 [SiO
0.9035(OH)
0.0549(OCH
3)
2.138]
7.707
S-3 1.0 97.2 1027 [SiO
0.9769(OH)
0.0585(OCH
3)
1.991]
9.650
S-4 1.1 99.2 1393 [SiO
1.0060(OH)
0.0727(OCH
3)
0.916]
13.29
S-5 1.2 99.8 2015 [SiO
1.3560(OH)
0.0935(OCH
3)
0.816]
27.16
Example 2: the preparation of polyacrylamide methyl siloxane (PAMOS)
Add HEA 9.28g (0.08mol), catalyst dibutyl tin laurate 200ppm and catalyst hydroquinone monomethyl ether 200ppm among the 10g PMOS (S-3), after being heated to 90 ℃ of reaction 12h, unreacted HEA decompression is removed, cooling, obtain the product P AMOS 15.02g of achromaticity and clarification, the conversion ratio 74.84% of HEA.Through characterizing the afterproduct molecular weight is 1543, and molecular structure can be expressed as [SiO
0.907(OH)
0.153(OCH
3)
1.385(OCH
2CH
2OCOCH=CH
2)
0.648]
9.486
The 10g PMOS (S-3) of same weight adds the HEA of Different Weight, and the molecular weight of products therefrom PAMOS is different with structure, and is as shown in table 2.
Molecular weight and the molecular formula of the product P AMOS of table 2 differential responses proportioning gained
PAMO HEA/S-3 weight molecule formula
S (weight Mn
ratio)
SE-1 0.232 1198 [SiO
0.972(OH)
0.043(OCH
3)
1.826(OCH
2CH
2OCOCH＝CH
2)
0.188]
9.769
SE-2 0.464 1389 [SiO
0.951(OH)
0.067(OCH
3)
1.667(OCH
2CH
2OCOCH＝CH
2)
0.365]
10.06
SE-3 0.703 1519 [SiO
0.950(OH)
0.137(OCH
3)
1.438(OCH
2CH
2OCOCH＝CH
2)
0.525]
10.10
SE-4 1.044 1683 [SiO
0.938(OH)
0.118(OCH
3)
1.402(OCH
2CH
2OCOCH＝CH
2)
0.604]
10.65
SE-5 1.740 1907 [SiO
0.964(OH)
0.074(OCH
3)
1.285(OCH
2CH
2OCOCH＝CH
2)
0.712]
11.45
The preparation of example 3 gel state inorganic-organic hybridization polymer dielectrics
The light trigger Iragacure 184 of SE-2 and 5wt.% mixes, again with the lithium ion battery liquid electrolyte (1MLiPF of different amounts
6, EC: DEC: DMC=1: 1: 1w/w) mix, splash in the stainless steel button battery case, through ultraviolet lighting 0.5-3 minute.With the gel polymer electrolyte of preparation in the button cell shell, cover stainless steel cover, encapsulation, testing conductivity then.The results are shown in Table 4.
Table 4 gel polymer electrolyte is formed and room-temperature conductivity
Numbering polymer content liquid electrolyte content room-temperature conductivity
1M?LiPF
6，EC∶DEC∶DMC＝1∶1∶1 (Scm
-1)
w/w
1
# 5wt.％ 95wt.％ 8.42×10
-3
2
# 10wt.％ 90wt.％ 3.59×10
-3
3
# 20wt.％ 80wt.％ 4.23×10
-3
4
# 30wt.％ 70wt.％ 2.69×10
-3
5
# 50wt.％ 50wt.％ 6.22×10
-4
6
# 70wt.％ 30wt.％ 8.36×10
-5
7
# 90wt.％ 10wt.％ 3.12×10
-5
The preparation of example 4 gel state inorganic-organic hybridization polymer dielectrics
575 PEGDA 1.0g, the lithium ion battery liquid electrolyte (1MLiPF that with PAAOS sample SE-3 1.0g, molecular weight are
6, EC: DEC: DMC=1: 1: 1w/w) 18.0g and Iragaeure 184 0.1g mix, and splash in the stainless steel button battery case, through 500 watts of high voltage mercury lamp radiation 2min.With the gel polymer electrolyte of preparation in the button cell shell, cover stainless steel cover, encapsulation, testing conductivity is 3.1 * 10 then
-3S cm
-1
Comparative example 1
575 PEGDA 1.0g, the lithium ion battery liquid electrolyte (1MLiPF that with PAAOS sample SE-3 1.0g, molecular weight are
6, EC: DEC: DMC=1: 1: 1w/w) 38.0g and Iragacure 184 0.1g mix, and splash in the stainless steel button battery case, through 500 watts of high voltage mercury lamp radiation 3min.Though it is big that mixed liquor viscosity becomes, but still can flow, can't gelation.
Claims (13)
1, a kind of chargeable lithium ion battery polymer dielectric is characterized in that this is electrolytical composed as follows:
The polymer that polyacrylate based oxyalkylsiloxane (PAAOS) forms: 5-90wt.%;
Chargeable lithium ion battery liquid electrolyte: 10-95wt.%;
The structure of PAAOS formula [SiO
d(OH)
e(OR
2)
f(O (CH
2CH
2O)
nCOCR
1=CH
2)
g]
kExpression, R
1=H or CH
3, n=1～7, R
2=CH
3, CH
2CH
3
2, chargeable lithium ion battery polymer dielectric according to claim 1 is characterized in that this is electrolytical composed as follows:
The polymer that PAAOS and polyethyleneglycol diacrylate (PEGDA) form: 8-90wt.%;
PEGDA accounts in the polymer that forms: 17-67wt.%;
Chargeable lithium ion battery liquid electrolyte: 10-92wt.%;
The molecular formula of PEGDA: CH
2=CR
1COO (CH
2CH
2O)
nCOCR
1=CH
2, R wherein
1=H or CH
3, n=3～16.
3, a kind of chargeable lithium ion battery method for preparing polymer electrolytes is characterized in that this electrolyte gets the ultraviolet light polymerization prescription by PAAOS, ultraviolet initiator and chargeable lithium ion battery liquid electrolyte through the ultraviolet radiation preparation:
PAAOS：5-90wt.％
Chargeable lithium ion battery liquid electrolyte: 6-95wt.%;
The consumption of light trigger is the 4-8wt.% of PAAOS weight.
4, chargeable lithium ion battery method for preparing polymer electrolytes according to claim 3 is characterized in that adding an amount of polyethyleneglycol diacrylate (PEGDA) in the reactant, and the addition of PEGDA accounts for the 17-67wt% of polymerisable monomer weight.
5, the preparation method of chargeable lithium ion battery polymer electrolyte according to claim 3, it is characterized in that the ultraviolet light polymerization initator is 1-hydroxy-cyclohexyl acetophenone or α, alpha-alpha-dimethyl-Alpha-hydroxy acetophenone, consumption are the 4-8wt.% of polymerisable monomer weight.
6, chargeable lithium ion battery method for preparing polymer electrolytes according to claim 3 is characterized in that uviol lamp power is 20-100W/cm, and atmosphere temperature is 10-70 ℃, light application time 0.5-3min.
7, chargeable lithium ion battery method for preparing polymer electrolytes according to claim 3, the preparation method who it is characterized in that prepolymer polyacrylate based oxyalkylsiloxane (PAAOS): gather oxyalkylsiloxane (PAOS) by the sol gel reaction preparation with alkoxy-silicon compound, then the part alkoxyl end group that will gather oxyalkylsiloxane with the acrylate compounds of hydroxyl be converted to acrylate-based, thereby obtain ultraviolet curing prepolymer polyacrylate based oxyalkylsiloxane (PAAOS);
Alkoxy-silicon compound is methyl silicate (TMOS) or tetraethoxysilane (TEOS), and molecular formula is respectively Si (OCH
3)
4, Si (OCH
2CH
3)
4
The structure of PAOS formula [SiO
a(OH)
b(OR)
c]
nExpression, R=CH
3, CH
2CH
3
The acrylate compounds structural formula of hydroxyl is: HO (CH
2CH
2O)
nCOCR
1=CH
2, R wherein
1=H or CH
3, n=1～7.
8, the preparation method of prepolymer polyacrylate based oxyalkylsiloxane according to claim 7 (PAAOS), it is characterized in that being prepared as follows of poly-oxyalkylsiloxane (PAOS): alkoxy-silicon compound makes by sol gel reaction under solvent, catalyst, the water yield that adds during the alkoxide compound hydrolytic condensation is 0.4-1.6 a times of alkoxide compound molal quantity, catalyst is acid or alkali, and consumption is 1 * 10 of an alkoxide compound molal quantity
-5To 1 * 10
-3Doubly, reaction dissolvent is alcohol or ether or ketone, and consumption is 0.1-10 a times of alkoxide compound molal quantity, reaction time 0.1-10 hour.
9, the preparation method of poly-oxyalkylsiloxane according to claim 8 (PAOS), the water yield that adds when it is characterized in that the alkoxy-silicon compound hydrolytic condensation are 0.8-1.2 times of its molal quantity.
10, the preparation method of poly-oxyalkylsiloxane according to claim 8 (PAOS) is characterized in that reaction dissolvent is an alcohol, and consumption is 0.5-1 a times of alkoxy-silicon compound weight.
11, the preparation method of poly-oxyalkylsiloxane according to claim 8 (PAOS) is characterized in that reaction time 1-5 hour.
12, the preparation method of prepolymer polyacrylate based oxyalkylsiloxane according to claim 7 (PAAOS), it is characterized in that alkoxyl end group that acrylate compounds with hydroxyl will gather oxyalkylsiloxane (PAOS) is converted to when acrylate-based, the acrylate compounds consumption of hydroxyl is 1-8 a times of PAOS molal quantity, reaction temperature 80-90 ℃, catalyst is the organic tin compound, and polymerization inhibitor is quinone or ether or phenol.
13, according to claim 1, the application that 3 described chargeable lithium ion battery polymer dielectrics and material thereof can fill lithium or lithium ion battery electrolyte as preparation.
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| CN102324303A (en) * | 2011-06-20 | 2012-01-18 | 华东师范大学 | Gel electrolyte of hybrid polymer and preparation method thereof |
| CN102412378A (en) * | 2011-09-28 | 2012-04-11 | 哈尔滨工业大学 | Polymer electrolyte isolating membrane, preparation method and use thereof |
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2003
- 2003-10-10 CN CNB2003101078490A patent/CN1295810C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102324303A (en) * | 2011-06-20 | 2012-01-18 | 华东师范大学 | Gel electrolyte of hybrid polymer and preparation method thereof |
| CN102324303B (en) * | 2011-06-20 | 2012-11-21 | 华东师范大学 | Gel electrolyte of hybrid polymer and preparation method thereof |
| CN102412378A (en) * | 2011-09-28 | 2012-04-11 | 哈尔滨工业大学 | Polymer electrolyte isolating membrane, preparation method and use thereof |
| CN113471530A (en) * | 2021-07-28 | 2021-10-01 | 西安交通大学 | Preparation method and application of inorganic clay array |
| CN113471530B (en) * | 2021-07-28 | 2022-10-25 | 西安交通大学 | Preparation method and application of inorganic clay array |
| CN113410516A (en) * | 2021-08-02 | 2021-09-17 | 清远萨菲安新材料有限公司 | Organic silicon electrolyte and preparation method and application thereof |
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